Palladium-catalysed C–H arylation of benzophospholes with aryl halides

Abstract

A palladium-catalysed C–H arylation of benzophospholes with aryl halides has been developed. The reaction with aryl iodides and bromides proceeds well even under phosphine ligand-free Pd(OAc)₂ catalysis whereas the Pd(PCy₃)₂ is effective for the coupling with less reactive aryl chlorides. The optimal conditions are also applicable to the double arylations with organic dihalides and annulation reaction with ortho-dihalogenated benzenes, making the corresponding benzophosphole-based acceptor–donor–acceptor-type molecules and highly condensed heteroacene-type molecules of potent interest in materials chemistry. Although there are many reports of catalytic C–H functionalisations of related benzoheteroles such as indoles, benzothiophenes, and benzofurans, this is the first successful example of the catalytic direct C–H transformation of benzophospholes, to the best of our knowledge. The preliminary optoelectronic properties of some newly synthesized benzophosphole derivatives are also investigated.